CN103788307B - Preparation method of concrete slump retaining agent based on allyl polyoxyethylene ether - Google Patents
Preparation method of concrete slump retaining agent based on allyl polyoxyethylene ether Download PDFInfo
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- CN103788307B CN103788307B CN201210436973.0A CN201210436973A CN103788307B CN 103788307 B CN103788307 B CN 103788307B CN 201210436973 A CN201210436973 A CN 201210436973A CN 103788307 B CN103788307 B CN 103788307B
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- polyoxyethylene ether
- polyethenoxy ether
- slump retaining
- retaining agent
- allyl polyethenoxy
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Abstract
The invention discloses a preparation method of a concrete slump retaining agent based on allyl polyoxyethylene ether. The method comprises the following steps: with the allyl polyoxyethylene ether, end group modified allyl polyoxyethylene ether and unsaturated carboxylic acid as main raw materials, reacting by adopting an aqueous polymerization process in the presence of an aid, and neutralizing until the pH value is proper so as to obtain the slump retaining agent with proper weight-average molecular weight. According to the method, the wide-source and low-price allyl polyoxyethylene ether and derivatives of the allyl polyoxyethylene ether are adopted as raw materials, and the concrete slump retaining agent with good slump retaining capability is obtained through a relatively simple and convenient production process.
Description
Technical field
The present invention relates to a kind of preparation method of the concrete slump retaining agent based on allyl polyethenoxy ether it is adaptable to general
Flow-through polycarboxylic acids water reducing agent compositional uses, and belongs to technical field of macromolecules.
Technical background
Over nearly 10 years, the high performance concrete water reducer with poly carboxylic acid series water reducer as representative is widely used in high ferro, municipal administration
In the key projects such as engineering, water conservancy construction, it has also become the emphasis direction of water reducer development and focus forward position in following a period of time.
At present, to be primarily present fresh concrete liquidity value added too fast for the polycarboxylate water-reducer product on market, that is, produce
Product protect the not enough problem of collapsing property.Common solution has：1. select the unsaturated monomer of novel high-activity, such as isopentene group gathers
Oxygen vinyl Ether/methyl allyl polyoxyethylene ether, replaces conventional allyl polyethenoxy ether, in order to improve between different monomers
Copolymerization rate, improve the tactical rule of polycarboxylate water-reducer molecule.(referring to United States Patent (USP) US7691921B2) the method uses
Raw material isopentene group polyoxyethylene ether/methyl allyl polyoxyethylene ether relatively costly.2. introduce new sustained release type and protect the work(that collapses
Energy monomer, such as Polyethylene Glycol unsaturation dibasic acid esters, three esters, polyester, polycarboxylic acids intermolecular forming part cross-linked structure, adjust water reducer
The release of molecule, adsorption dynamics adsorption kinetics process, optimize the function of slump protection of polycarboxylate water-reducer molecule.The method is related to new function list
Pre-prepared, the complex operation of body.(referring to Chinese patent CN101831037A) 3. individually develops new function and protects agent of collapsing,
Using mix outward or interior incorporation plain edition polycarboxylate water-reducer by the way of, improve it and protect and collapse performance.As gathering that certain company external releases
The special guarantor of carboxylic acid water reducer is collapsed agent, but the development difficulty of the method is relatively large.
Content of the invention
It is an object of the invention to provide a kind of preparation method of concrete slump retaining agent.The method is low with wide material sources, price
Honest and clean allyl polyethenoxy ether and its derivant are raw material, by the production technology of relative ease, obtain thering is good slump
The new concrete slump retaining agent of degree holding capacity, thus effectively solving current plain edition polycarboxylate water-reducer concrete slump retaining performance
Not enough problem.
For achieving the above object, the technical solution used in the present invention is as follows：
With allyl polyethenoxy ether, terminal groups modification allyl polyethenoxy ether and unsaturated carboxylic acid as primary raw material,
In the presence of auxiliary agent, using polymerizable aqueous technological reaction, and it is neutralized to suitable pH, thus obtaining that there is appropriate weight average molecular weight
Slump retaining agent；
Allyl polyethenoxy ether structure is as follows, and molecular weight is 1500-5000, accounts for primary raw material gross mass 40-70%；
Modified allyl polyethenoxy ether structure is as follows, and molecular weight is 400-2000, accounts for primary raw material gross mass 15-
40%；
Wherein, the chemical constitution of A is as follows chemical constitution and its corresponding solubility ammonium salt, alkali metal salt or right
The acid salt answered；
Unsaturated carboxylic acid is (methyl) acrylic acid, itaconic acid, maleic acid (acid anhydride) unitary or multi-unsaturated carboxylic acid or anhydride,
Account for primary raw material gross mass 5-25%；
Auxiliary agent includes Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate, hydrogen peroxide, tert-butyl hydroperoxide, benzoyl peroxide first
Acyl, azodiisobutyronitrile, azo diisobutyl amidine hydrochlorate, azo two isobutyl imidazoline hydrochloride, azo dicyano valeric acid, idol
Nitrogen diisopropyl imidazoline, sodium sulfite, sodium sulfite, hypophosphorous acid (sodium), ferrous sulfate, Vc, different Vc, mercaptoethanol, mercapto
Guanidine-acetic acid, 2 mercaptopropionic acid, the combination of one or more of 3- mercaptopropionic acid, its consumption is primary raw material gross mass used
0.1-3%；
Using polymerizable aqueous technique parameter be 20-100 DEG C of polymerization temperature, polymerization concentration 5-90%, polymerization time
0.5h-10h, monomer dropping work mode includes single tube Deca, two-tube Deca, multitube Deca technique；
The temperature of neutralization is 20-60 DEG C, and the nertralizer of use is sodium hydroxide, potassium hydroxide, potassium hydroxide；
Weight average molecular weight 15000-100000 of concrete slump retaining agent, pH is 3-9, and solid content is 5-90%.
The present invention is claimed the concrete slump retaining agent that above-mentioned preparation method obtains simultaneously.
The know-why of the present invention：
Due to allyl group distinctive " pi-allyl is from inhibition " effect, under conventional polymerizable aqueous process conditions, long
(molecular weight is 1500-5000 to the allyl polyethenoxy ether of side chain, and the molecular weight product generally 2400 of domestic commerce is left
Right) there is relatively low polymerization activity, when reacting with the unsaturated carboxylic acid (as acrylic acid etc.) of active small-molecular-weight,
Copolymerization is less efficient.The terminal groups modification allyl polyethenoxy ether (molecular weight is 400-2000) of short-side chain has sky conveniently
Between stereochemical structure and polyreaction activation energy, on the one hand polymerization process can be participated in as effective reaction media, improve
The efficiency of initiation of system, on the other hand significantly improves the allyl polyethenoxy ether of long side chain and unsaturated carboxylic acid two class monomer
Copolymerization rate and polymerisation conversion, thus be obtained the compact type pectination polycarboxylic acids molecule with high sequence regularity.In reality
In the application process of border, the polycarboxylic acids molecule displays with this structure have gone out good function of slump protection.
Compared with prior art, this method has advantages below：
1., with allyl polyethenoxy ether and its derivant as primary raw material, the structure with high sequence regularity has been obtained
Compact pectination polycarboxylic acids molecule, shows good function of slump protection；
2. this invention has the characteristics that raw material sources are extensive, with low cost, production technology is easy, and being suitable to further genralrlization makes
With.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described：
Embodiment one：
In 1L glass flask, add 220g deionized water, 240g allyl polyethenoxy ether APEG-2400 (molecular weight
2400), 120g allyl polyethenoxy ether ichthyodin ASPEG-1200 (molecular weight 1200), mix homogeneously.Open stirring, heat up
To 85 DEG C.Start Deca monomer solution respectively (to consist of：45g acrylic acid+180g deionized water) and initiator solution (composition
For：4g sodium peroxydisulfate+220g deionized water), uniform completion of dropping in 3 hours.After 85 DEG C of insulation 1h, solution is cooled to 40-
50℃.Add 32%NaOH, adjustment system is to pH5.8-6.2, the guarantor that prepared weight average molecular weight is 35000, solid content is 40%
Collapse agent SP-A.
Embodiment two：
In 1L glass flask, add 220g deionized water, 240g allyl polyethenoxy ether APEG-2400 (molecular weight
2400), 120g allyl polyethenoxy ether mono phosphonic acid disodium APPEG-1200 (molecular weight 1200), mix homogeneously.Open stirring,
It is warming up to 85 DEG C.Start to be added dropwise to monomer solution respectively and (consist of：45g acrylic acid+180g deionized water) and initiator solution
(consist of：4g sodium peroxydisulfate+220g deionized water), uniform completion of dropping in 3 hours.After 85 DEG C of insulation 1h, solution is lowered the temperature
To 40-50 DEG C.Add 32%NaOH, to pH5.8-6.2, prepared weight average molecular weight is 38000, solid content is 40% to adjustment system
Slump retaining agent SP-B.
Application Example：
According to GB 8076-2008《Concrete admixture》Relevant regulations, collapsing of this product is detected using concrete test
Degree of falling, the performance parameter such as slump-retaining.Wherein, comparative sample PC-1 of employing is (to be divided based on allyl polyethenoxy ether
Son amount 1200) plain edition polycarboxylate water-reducer, PC-2 is the plain edition based on allyl polyethenoxy ether (molecular weight 2400)
Polycarboxylate water-reducer, concrete mix and application effect related data are as shown in table 1,2.
Table 1 concrete mix (kg/m3)
| C | S | G | FA | W | Water reducer volume |
| 301 | 816 | 1039 | 69 | 165 | 0.24% × C |
Note：C is 42.5 grades of the cement P O in Ji east；S is natural river sand；G is rubble 5-31.5mm；FA is Huaneng Group I level fine coal
Ash；W is tap water.
Table 2 concrete application effect related data
From above-mentioned data, the slump retaining agent synthesized by the present invention has more excellent slump-retaining energy.
The foregoing is only the preferred embodiments of the present invention, not thereby limit the scope of the claims of the present invention, every utilization
Equivalent structure or equivalent flow conversion that description of the invention and accompanying drawing content are made, or it is related to be directly or indirectly used in other
Technical field, be included within the scope of the present invention.
Claims (1)
1. a kind of preparation method of the concrete slump retaining agent based on allyl polyethenoxy ether it is characterised in that：
With allyl polyethenoxy ether, terminal groups modification allyl polyethenoxy ether and unsaturated carboxylic acid as primary raw material, in auxiliary agent
In the presence of, using polymerizable aqueous technological reaction, and it is neutralized to suitable pH, thus the guarantor obtaining having appropriate weight average molecular weight is collapsed
Agent,
Wherein, allyl polyethenoxy ether structure is as follows, and molecular weight is 1500-5000, accounts for the 40- of primary raw material gross mass
70%；
Modified allyl polyethenoxy ether structure is as follows, and molecular weight is 400-2000, accounts for the 15-40% of primary raw material gross mass；
Wherein, the chemical constitution of A is as follows chemical constitution and its corresponding solubility ammonium salt, alkali metal salt or corresponding
Acid salt,
.
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| CN104004144A (en) * | 2014-05-16 | 2014-08-27 | 北京市新世纪东方建筑材料有限公司 | Synthesis method of high-slump-retaining polycarboxylate superplasticizer |
| CN105949404A (en) * | 2016-06-04 | 2016-09-21 | 石家庄市长安育才建材有限公司 | Preparation method of slump retaining agent capable of releasing controllable polycarboxylic acid |
| CN109320126A (en) * | 2017-08-01 | 2019-02-12 | 辽宁煜梽新型建材有限公司 | A kind of production method of concrete admixture |
| CN107446089B (en) * | 2017-08-09 | 2019-10-01 | 武汉理工大学 | One kind is drawn money on credit chain end group esterification modification polycarboxylate water-reducer and preparation method thereof |
| CN108164173A (en) * | 2017-12-11 | 2018-06-15 | 湖北麦斯合普新材料股份有限公司 | A kind of concrete slump retaining agent and preparation method thereof |
| CN108752538A (en) * | 2018-06-28 | 2018-11-06 | 江苏百瑞吉新材料有限公司 | A kind of high overlength of system containing mud guarantor is collapsed concrete tailored version poly carboxylic acid series water reducer |
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| CN102120805A (en) * | 2011-01-27 | 2011-07-13 | 南京瑞迪高新技术公司 | Method for preparing slump-retaining type polycarboxylic acid series high-performance water reducing agent in one step |
| CN102286134A (en) * | 2011-06-09 | 2011-12-21 | 江苏天音化工有限公司 | Preparation method for high-performance water reducing agent |
| CN102358768A (en) * | 2011-07-22 | 2012-02-22 | 广州市建筑科学研究院有限公司 | Modified ether polycarboxylic acid water reducing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102120805A (en) * | 2011-01-27 | 2011-07-13 | 南京瑞迪高新技术公司 | Method for preparing slump-retaining type polycarboxylic acid series high-performance water reducing agent in one step |
| CN102286134A (en) * | 2011-06-09 | 2011-12-21 | 江苏天音化工有限公司 | Preparation method for high-performance water reducing agent |
| CN102358768A (en) * | 2011-07-22 | 2012-02-22 | 广州市建筑科学研究院有限公司 | Modified ether polycarboxylic acid water reducing agent and preparation method thereof |
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